KR100819761B1 - Tetrakisphenyl Compounds And Organic Elecroluminescence Devices Using The Same - Google Patents

Abstract

  An object of the present invention is to provide an organic electroluminescent device having excellent stability and luminous efficiency of a device by using a tetrahedral (Tetrahedral, Th) light emitting material. Accordingly, the present invention provides an organic electroluminescent device comprising a compound having a tetrahedral (Th) structure of the following formula as a blue light emitting material of an organic light emitting layer in the construction of an organic light emitting device comprising a first electrode, an organic light emitting layer and a second electrode. To provide.

In the above formula, A is a carbon atom or a silicon atom, R is an oxygen atom or the following formula.

N is an integer of 0 to 3, Ar ₁ may be selected from the group consisting of aromatic substituents. Ar ₁ may also be selected from a phenyl group, a naphthyl group, anthracenyl group, and a phenanthrenyl group.

Blue light emitting material, Th structure, organic electroluminescent device  

Description

Tetrakisphenyl Compounds and Organic Elecroluminescence Devices Using The Same}

  1 is a structural cross-sectional view of an organic light emitting display device according to the present invention.

The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device comprising a compound having a tetraphenylmethane or tetraphenylsilane structure as a blue light emitting material of the organic light emitting layer.

Recently, as the size of the display device increases, the demand for a flat display device having less space is increasing. As one of the flat display devices, an organic light emitting diode (OLED), also called an organic light emitting diode (OLED), has recently been rapidly developed. It is evolving at a rate, and several prototypes have already been announced.

The organic light emitting display combines electrons and holes by injecting electrons and holes into an organic light emitting layer formed between a first electrode (anode), which is a hole injection electrode (anode), and a second electrode (cathode), which is an electron injection electrode (cathode), respectively. Excitons formed in pairs fall from the excited state to the ground state, and the energy difference between them is converted into light and emits light.

Such organic electroluminescent devices have an advantage that they can be driven at a lower voltage (eg, 10V or less) than plasma display panels (PDPs) or inorganic electroluminescent device displays.

Organic electroluminescent devices have excellent features such as wide viewing angle, high speed response and high contrast, so they can be used as pixels in graphic displays, television image displays or surface light sources. In addition, since the device can be formed on a flexible transparent substrate such as plastic, it can be made very thin and light, and the color is good, it is suitable for the next-generation flat panel display (FDP).

In addition, it can display three colors of green, blue, and red, and requires less backlight than the well-known liquid crystal display (LCD), which consumes less power. In addition, it is excellent in color and is attracting many people's attention as the next generation full color display device.

The manufacturing process of a general organic electroluminescent device is as follows.

First, an anode material is formed on a transparent substrate. Indium tin oxide (ITO) is commonly used as a cathode material.

A hole injection layer (HIL) is formed on the anode material. Copper phthalocyanine (CuPC: copper phthalocyanine) is mainly used as a hole injection layer, and the thickness is made into about 10 mm-30 mm.

Next, a hole transport layer (HTL) is introduced. The hole transport layer is formed by depositing NPD (4.4'-bis [N- (1-naphthyl) -N-phenylamino] -biphenyl) to a thickness of about 30 mm to 60 mm.

And an organic light emitting layer (Organic Emitting Layer) is formed on the hole transport layer. At this time, a dopant is added to the organic light emitting layer as necessary.

For example, in the case of green light emission, Alq3 (tris (3-hydroxy-quinolate) -aluminum) is often deposited as an organic light emitting layer to a thickness of about 30 mm to 60 mm, and impurities such as MQD (N-Methylquinacridone) Write

Subsequently, an electron transport layer (ETL) and an electron injection layer (EIL) are formed continuously on the organic light emitting layer, or an electron injection transport layer is formed. In the case of green light emission, since Alq3 used as an organic light emitting layer has excellent electron transport ability, there are many cases where an electron injection / transport layer is not used.

Next, a cathode is formed on the electron injection layer, and finally a protective film is formed.

In general, in order to realize full-color with organic EL, a light emitting device that emits three colors of green, red, and blue is required.

The blue may be implemented by doping blue impurities into the blue host, using Alq3 as the electron transport layer ETL, and omitting Alq3 according to the characteristics of the blue host.

In the case of red, a red wavelength may be obtained by doping red impurities instead of green impurities during the device fabrication process.

However, in the case of the green light emitting device, the stability of the device has been evaluated to the practical use level, but in the case of the blue light emitting device, the emission color and the stability of the device are still not at the practical level, and the luminous efficiency thereof is not satisfactory. There is a problem.

    Therefore, the present invention has been invented for the purpose of solving the above problems, and the object of the present invention is to synthesize an organic light emitting device excellent in the stability and luminous efficiency of the device by synthesizing a new blue light emitting material.

    In order to achieve the above object, according to the present invention, an organic electroluminescent device comprising a first electrode, an organic light emitting layer and a second electrode, as a blue light emitting material of the organic light emitting layer Tetrahedral (Tetrahedral, hereinafter ' An organic electroluminescent device using a compound having a structure abbreviated Th 'is provided.

Formula 1

In the above formula, A is a carbon atom or a silicon atom, R is an oxygen atom or the following formula.

N is an integer of 0 to 3, Ar ₁ may be selected from the group consisting of aromatic substituents.

Ar ₁ may also be selected from a phenyl group, a naphthyl group, anthracenyl group, and a phenanthrenyl group.

In addition, the compound that can be used as a blue light emitting material of the organic light emitting material may be a compound consisting of the formula (2).

Formula 2

In the above formula, A is a carbon atom or a silicon atom.

1 is a structural cross-sectional view of an organic light emitting display device formed by the present invention. The above compound is used as a blue light emitting material of the organic light emitting layer. The compound of Formula 2 may be synthesized by the following method.

(1) Synthesis of tetra-p-benzoylphenylmethane

 Tetra-p-bromophenyl methane (6.36 g) is added to a round bottom flask and THF (300 ml) is dissolved in an argon atmosphere. The temperature is maintained at minus 78 degrees and 1.6 molar BuLi solution (300 ml) is added dropwise. Stir at the same temperature for 30 minutes and add dropwise a solution of benzaldehyde (4.5 g) in THF (100 ml). The temperature is raised to room temperature after 30 minutes of stirring at the same temperature. Add saturated ammonium chloride solution (300ml) and separate layers. The organic layer is separated to remove moisture and concentrated under reduced pressure. MC (300ml) was added to the residue, followed by PCC (17.25g), followed by stirring for 12 hours. The reaction solution was filtered, concentrated under reduced pressure, and recrystallized from a THF / methanol mixed solvent to obtain a labeled compound (6 g).

(2) Synthesis of tetra-p-benzoylphenylsilane

Tetra-p-bromophenyl silane (6.52 g) is added to a round bottom flask and THF (300 ml) is dissolved in an argon atmosphere. The temperature is maintained at minus 78 degrees and 1.6 molar BuLi solution (300 ml) is added dropwise. Stir at the same temperature for 30 minutes and add dropwise a solution of benzaldehyde (4.5 g) in THF (100 ml). The temperature is raised to room temperature after 30 minutes of stirring at the same temperature. Add saturated ammonium chloride solution (300ml) and separate layers. The organic layer is separated to remove moisture and concentrated under reduced pressure. MC (300ml) was added to the residue, followed by PCC (17.25g), followed by stirring for 12 hours. The reaction solution was filtered, concentrated under reduced pressure, and recrystallized from a THF / methanol mixed solvent to obtain a labeled compound (7 g).

(3) 4,4'-bis (diethoxyphosphonomethyl) -1,1'-biphenyl

   Synthesis of (4,4'-bis (diethoxyphosphonomethyl) -1,1'-biphenyl)

A mixed solution of 4,4'-bis (bromomethyl) -1,1'-biphenyl (34 g) and triethylphosphite (33.2 g) was added to ethanol (100 mL) for 24 hours. The mixed solution was cooled to room temperature, the solvent was distilled off under reduced pressure, and the reaction mixture was recrystallized from a mixed solvent of ethyl acetate: hexane (1: 1, volume ratio) to obtain a labeled compound (43 g).

(4) [4 '-(2,2-diphenylvinyl) biphenyl-4-methyl] phosphate diethyl ester

  Synthesis of ([4 '-(2,2-Diphenyl-vinyl) -biphenyl-4-methyl] -phosphonic acid diethyl ester)

4,4'-bis (diethoxyphosphonomethyl) -1,1'-biphenyl (9.1 g) was dissolved in THF (200 mL) in the presence of nitrogen, followed by 93.7 g of benzophenone and potassium t-butoxide ( 5.6 g) was added and stirred at a temperature of 40 ° C for 24 h. The mixed solution was cooled to room temperature, distilled water (200 mL) was added slowly, and then ethyl acetate (200 mL) was added to the solution, and the mixed organic solvent layer was separated. The organic solvent layer was dried over anhydrous magnesium sulfate, distilled, and the reaction mixture was recrystallized with dichloromethane to obtain a white solid labeled compound (10 g).

(5) tetrakis [4-((E) -2- (4 '-(2,2-diphenylvinyl) biphenyl-4-yl) -1-phenylvinyl) phenyl] methane (tetrakis [4- ( Synthesis of (E) -2- (4 '-(2,2-diphenylvinyl) biphenyl-4-yl) -1-phenylvinyl) pheny] methane)

Tetraparabenzoylphenylmethane (7.3 g) synthesized in step (1) in the presence of nitrogen and [4 '-(2,2-diphenylvinyl) biphenyl-4-methyl] phosphate synthesized in step (4) Diethyl ester (25 g) was dissolved in THF (200 mL), and potassium t-butoxide (15.6 g) was added and stirred at a temperature of 40 ° C. for 24 hours. The mixed solution was cooled to room temperature, distilled water (200 mL) was added slowly, and then ethyl acetate (200 mL) was added to the solution, and the mixed organic solvent layer was separated. The organic solvent layer was dried over anhydrous magnesium sulfate, distilled, and the reaction mixture was recrystallized with dichloromethane to obtain a white solid labeled compound (11 g).

(6) tetrakis [4-((E) -2- (4 '-(2,2-diphenylvinyl) biphenyl-4-yl) -1-phenylvinyl) phenyl] silane (tetrakis [4- ( Synthesis of (E) -2- (4 '-(2,2-diphenylvinyl) biphenyl-4-yl) -1-phenylvinyl) phenyl] silane)

Tetraparabenzoylphenylsilane (7.5 g) synthesized in step (2) in the presence of nitrogen and [4 '-(2,2-diphenylvinyl) biphenyl-4-methyl] phosphate synthesized in step (4) Diethyl ester (25 g) was dissolved in THF (200 mL), and potassium t-butoxide (5.6 g) was added and stirred at a temperature of 40 ° C. for 24 hours. The mixed solution was cooled to room temperature, distilled water (200 mL) was added slowly, and then ethyl acetate (200 mL) was added to the solution, and the mixed organic solvent layer was separated. The organic solvent layer was dried over anhydrous magnesium sulfate, distilled, and the reaction mixture was recrystallized with dichloromethane to obtain a white solid labeled compound (12 g).

As described in detail above, the present invention uses the compound of the tetrahedron (Th) structure as a blue light emitting material of the organic light emitting body to obtain an organic light emitting device having excellent light emission color and stability of the device and increased luminous efficiency. have.

Various changes and applications may be made by those skilled in the art through the above description without departing from the technical spirit of the present invention. Therefore, the technical scope of the present invention should not be limited to the contents disclosed in the embodiments, but should be defined by the claims.

Claims (8)

An organic electroluminescent device comprising a first electrode, an organic light emitting layer, and a second electrode, the organic light emitting device using a tetrahedral (Tetrahedral, Th) structure compound having the following formula as a blue light emitting material of the organic light emitting layer:

In the above formula, A is a carbon atom or a silicon atom, R is an oxygen atom or the following formula.

N is an integer of 0 to 3, Ar ₁ is selected from the group consisting of aromatic substituents. The method of claim 1, Ar ₁ is an organic electroluminescent device, characterized in that selected from the group consisting of phenyl group, naphthyl group, anthracenyl group and phenanthrenyl group. The method of claim 1, A is a carbon atom or a silicon atom, R is an oxygen atom, the organic electroluminescent device, characterized in that the compound of the formula:

The method of claim 3, wherein An organic electroluminescent device, wherein A is a compound of the formula:

The method of claim 3, wherein An organic electroluminescent device according to claim 1, wherein A is a silicon atom;

The method of claim 1, The compound is an organic electroluminescent device, characterized in that the tetrahedral (Th) structure compound of the formula:

A is a carbon atom or a silicon atom. The method of claim 6, The compound is an organic electroluminescent device, characterized in that the compound of the formula:

The method of claim 6, The compound is an organic electroluminescent device, characterized in that the compound of the formula:

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